Disinfectant cleaning compositions

ABSTRACT

The present invention provides a non-cationic antimicrobial agent containing composition which blooms when added to water. The compositions have good cleaning, disinfecting and bloom properties.

The present invention is directed to concentrated cleaning and/ordisinfecting compositions which bloom when diluted in water.

Cleaning compositions are commercially important products and enjoy awide field of utility in assisting in the removal of dirt and grime fromsurfaces, especially those characterized as useful with hard surfaces.One particular category of cleaning compositions are those which providea blooming effect. Such an effect may be described as the change of thewater's appearance from essentially colorless and transparent to that ofa milky white or milky yellowish white, cloudy appearance upon theaddition of an amount of the cleaning composition. This effect is alsosometimes referred to as the “break”. Such blooming is a highlydesirable in such pine oil type cleaning compositions as consumer/enduser expectations associate cleaning effectiveness/disinfection with theextent and degree of this blooming upon formation of a cleaningcomposition. Such an effect is particularly known and generallyassociated with pine oil type cleaning compositions which typicallyinclude one or more of the following identifying characteristics:containing an amount of one or more resins or oils derived fromconiferous species of trees; containing natural fragrances or syntheticfragrance compositions which are intended to mimic the scent of one ormore resins or oils derived from coniferous species of trees; a colorranging from colorless to a deep amber, deep amber yellow or deep amberreddish color; generation of a milky or cloudy appearance when dilutedwith water in dilutions useful for cleaning applications. Such pine oiltype cleaning compositions are generally provided in a concentratedcomposition which is subsequently diluted with water by an enduser/consumer to form a cleaning composition therefrom.

Thus, the present invention provides a hard surface cleaning concentratecomposition comprising:

-   -   a) from about 0.05 to about 15 wt %, preferably about 0.1 to        about 5 wt %, and more preferably from about 0.5 to about 5 wt %        of a non-cationic antimicrobial agent;    -   b) from about 0.1 to about 20 wt % and more preferably from        about 0.5 to about 10 Wt % of a water soluble organic solvent;    -   c) from about 0.1 to about 30 wt %, preferably from about 1 to        about 20 wt %, and more preferably from about 2 to about 15 wt %        of an anionic soap surfactant;    -   d) from about 0.1 to about 15 wt %, preferably from about 0.1 to        about 10 wt %, and more preferably from about 0.5 to about 5 wt        % of an hydrocarbon diluent;    -   e) from about 0.001 to about 10 wt %, preferably from about 0.1        to about 5 wt %, and more preferably from about 0.5 to about 5        wt % of pine oil which is at least 60% terpene alcohols;    -   f) optionally, from about 0 to about 10 wt % of optional        materials selected from dyes, colorants, pH stabilizers and        buffers, non-ionic surfactants, fragrance/fragrance enhancers        which do not interfere with the pine oil constituent, viscosity        modifiers, insect repellants, and light stabilizers; and    -   g) the balance being water.

In some preferred embodiments, one or more insect repellants is present.

Preferably, the non-cationic antimicrobial agent is selected frompyrithiones, dimethyldimethylol hydantoin,methylchloroisothiazolinone/methylisothiazolinone sodium sulfite, sodiumbisulfite, imidazolidinyl urea, diazolidinyl urea, benzyl alcohol,2-bromo-2-nitropropane-1,3-diol, formalin (formaldehyde), iodopropenylbutylcarbamate, chloroacetamide, methanamine, methyldibromonitrileglutaronitrile, glutaraldehyde, 5-bromo-5-nitro-1,3-dioxane, phenethylalcohol, o-phenylphenol/sodium o-phenylphenol, sodiumhydroxymethylglycinate, polymethoxy bicyclic oxazolidine, dimethoxane,thilersal dichlorobenzyl alcohol, captan, chlorphenenesin,dichlorophene, chlorbutanol, glyceryl laurate, halogenated diphenylethers, phenolic compounds, mono- and poly-alkyl and aromatichalophenols, resorcinol and its derivatives, bisphenolic compounds,benzoic esters (parabens), halogenated carbanilides,3-trifluoromethyl-4,4′-dichlorocarbanilide, and 3,3′,4trichlorocarbanilide. More preferably, the non-cationic antimicrobialagent is a mono- and poly-alkyl and aromatic halophenol selected fromthe group p-chlorophenol, methyl p-chlorophenol, ethyl p-chlorophenol,n-propyl p-chlorophenol, n-butyl p-chlorophenol, n-amyl p-chlorophenol,sec-amyl p-chlorophenol, n-hexyl p-chlorophenol, cyclohexylp-chlorophenol, n-heptyl p-chlorophenol, n-octyl p-chlorophenol,o-chlorophenol, methyl o-chlorophenol, ethyl o-chlorophenol, n-propylo-chlorophenol, n-butyl o-chlorophenol, n-amyl o-chlorophenol, tert-amylo-chlorophenol, n-hexyl o-chlorophenol, n-heptyl o-chlorophenol,o-benzyl p-chlorophenol, o-benzyl-m-methyl p-chlorophenol, o-benzyl-m,m-dimethyl p-chlorophenol, o-phenylethyl p-chlorophenol,o-phenylethyl-m-methyl p-chlorophenol, 3-methyl p-chlorophenol,3,5-dimethyl p-chlorophenol, 6-ethyl-3-methyl p-chlorophenol,6-n-propyl-3-methyl p-chlorophenol, 6-iso-propyl-3-methyl p-chlorophenol2-ethyl-3,5-dimethyl p-chlorophenol, 6-sec-butyl-3-methylp-chlorophenol, 2-iso-propyl-3,5-dimethyl p-chlorophenol,6-diethylmethyl-3-methyl p-chlorophenol, 6-iso-propyl-2-ethyl-3-methylp-chlorophenol, 2-sec-amyl-3,5-dimethyl p-chlorophenol2-diethylmethyl-3,5-dimethyl p-chlorophenol, 6-sec-octyl-3-methylp-chlorophenol, p-chloro-m-cresol, p-bromophenol, methyl p-bromophenol,ethyl p-bromophenol, n-propyl p-bromophenol, n-butyl p-bromophenol,n-amyl p-bromophenol, sec-amyl p-bromophenol, n-hexyl p-bromophenol,cyclohexyl p-bromophenol, o-bromophenol, tert-amyl o-bromophenol,n-hexyl o-bromophenol, n-propyl-m,m-dimethyl o-bromophenol, 2-phenylphenol, 4-chloro-2-methyl phenol, 4-chloro-3-methyl phenol,4-chloro-3,5-dimethyl phenol, 2,4-dichloro-3,5-dimethylphenol,3,4,5,6-terabromo-2-methylphenol, 5-methyl-2-pentylphenol,4-isopropyl-3-methylphenol, para-chloro-meta-xylenol, dichloro metaxylenol, chlorothymol, and 5-chloro-2-hydroxydiphenylmethane.

Preferably, the water soluble organic solvents are short chain alcohols.

Preferably, for the anionic soap surfactants, alkyl metal soaps andalkylaryl sulfonates are preferred with alkyl metal soaps, such assodium or potassium castor oil soap, being preferred.

Preferably, the hydrocarbon diluent is an aromatic hydrocarbon diluent,preferably selected from Shellsolv AB, Aromatic 150, Aromatic 200(naphthalene depleted), Aromatic 200, Aromatic 100, and HAN 857.

According to certain especially preferred embodiments, the concentratecompositions may be characterized in that when the concentratecompositions are diluted at a ratio of 1 part to 100 parts water at 20°C. or 40° C. the resultant mixture exhibits a light transmittance lossof at least 50%. In particularly preferred embodiments the concentratecompositions do not form a gel at usual storage conditions (roomtemperature, approx. 20° C.), and exhibit a satisfactory blooming effectwhen added to a larger volume of water where such water is either atroom temperature or at a higher temperature, particularly at approx. 40°C. According to preferred embodiments, the concentrate compositionscause a drop in transmitted light through water of at least 20%, moredesirably at least about 30% and more when used to form a cleaningcomposition therefrom, particularly at a dilution of 1 part cleaningconcentrate to 100 parts water relative to the transmittance of water,which is established to be 100%. According to particularly preferredembodiments the concentrate compositions cause a drop in transmittedlight through water of at least about 40% when added to water at 40° C.,and also cause a drop in transmitted light through water of at least40%, more desirably at least 50%, when added to water at 20° C. Mostpreferred are compositions which exhibit a drop in transmitted light ofat least 70% when added to water at 20° C., and which exhibit a drop intransmitted light of at least 60% when added to water at 40° C. whereinthe dilutions of concentrate composition to water is 1:100.

The antimicrobial agents of the present invention are non-cationic inorder to avoid interaction with the anionic soap surfactant of theinvention. Given below are examples of non-cationic antimicrobial agentswhich are useful in the present invention: pyrithiones (especially zincpyrithione which is also known as ZPT), dimethyldimethylol hydantoin(Glydant®), methylchloroisothiazolinone/methylisothiazolinone KathonCG®), sodium sulfite, sodium bisulfite, imidazolidinyl urea (Germall115®), diazolidinyl urea (Germaill II®), benzyl alcohol,2-bromo-2-nitropropane-1,3-diol (Bronopol®), formalin (formaldehyde),iodopropenyl butylcarbamate (Polyphase P100®), chloroacetamide,methanamine, methyldibromonitrile glutaronitrile(1,2-Dibromo-2,4-dicyanobutane or Tektamer®), glutaraldehyde,5-bromo-5-nitro-1,3-dioxane (Bronidox®), phenethyl alcohol,o-phenylphenol/sodium o-phenylphenol, sodium hydroxymethylglycinate(Suttocide A®), polymethoxy bicyclic oxazolidine (Nuosept C®),dimethoxane, thimersal dichlorobenzyl alcohol, captan, chlorphenenesin,dichlorophene, chlorbutanol, glyceryl laurate, halogenated diphenylethers like 2,4,4′-trichloro-2′-hydroxy-diphenyl ether (Triclosan® orTCS), 2,2′dihydroxy-5,5′-dibromo-diphenyl ether, phenolic compounds likephenol 2-methyl phenol 3-methyl phenol, 4-methyl phenol, 4-ethyl phenol,2,4-dimethyl phenol, 2,5-dimethyl phenol, 3,4-dimethyl phenol,2,6-dimethyl phenol, 4-n-propyl phenol 4-n-butyl phenol 4-n-amyl phenol,4-tert-amyl phenol, 4-n-hexyl phenol, 4-n-heptyl phenol, mono- andpoly-alkyl and aromatic halophenols such as p-chlorophenol, methylp-chlorophenol ethyl p-chlorophenol, n-propyl p-chlorophenol, n-butylp-chlorophenol, n-amyl p-chlorophenol, sec-amyl p-chlorophenol n-hexylp-chlorophenol, cyclohexyl p-chlorophenol, n-heptyl p-chlorophenol,n-octyl p-chlorophenol, o-chlorophenol, methyl o-chlorophenol, ethylo-chlorophenol, n-propyl o-chlorophenol, n-butyl o-chlorophenol, n-amylo-chlorophenol, tert-amyl o-chlorophenol, n-hexyl o-chlorophenol,n-heptyl o-chlorophenol o-benzyl p-chlorophenol, o-benzyl-m-methylp-chlorophenol, o-benzyl-m, m-dimethyl p-chlorophenol, o-phenylethylp-chlorophenol, o-phenylethyl-m-methyl p-chlorophenol, 3-methylp-chlorophenol, 3,5-dimethyl p-chlorophenol, 6-ethyl-3-methylp-chlorophenol, 6-n-propyl-3-methyl p-chlorophenol,6-iso-propyl-3-methyl p-chlorophenol, 2-ethyl-3,5-dimethylp-chlorophenol, 6-sec-butyl-3-methyl p-chlorophenol,2-iso-propyl-3,5-dimethyl p-chlorophenol 6-diethylmethyl-3-methylp-chlorophenol, 6-iso-propyl-2-ethyl-3-methyl p-chlorophenol,2-sec-amyl-3,5-dimethyl p-chlorophenol 2-diethylmethyl-3,5-dimethylp-chlorophenol, 6-sec-octyl-3-methyl p-chlorophenol, p-chloro-m-cresol,p-bromophenol, methyl p-bromophenol ethyl p-bromophenol, n-propylp-bromophenol, n-butyl p-bromophenol n-amyl p-bromophenol sec-amylp-bromophenol, n-hexyl p-bromophenol, cyclohexyl p-bromophenol,o-bromophenol, tert-amyl o-bromophenol n-hexyl o-bromophenol,n-propyl-m,m-dimethyl o-bromophenol, 2-phenyl phenol, 4-chloro-2-methylphenol, 4-chloro-3-methyl phenol, 4-chloro-3,5-dimethyl phenol,2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-terabromo-2-methylphenol,5-methyl-2-pentylphenol, 4-isopropyl-3-methylphenol,para-chloro-meta-xylenol, dichloro meta xylenol, chlorothymol,5-chloro-2-hydroxydiphenylmethane, resorcinol and its derivativesincluding methyl resorcinol, ethyl resorcinol, n-propyl resorcinol,n-butyl resorcinol, n-amyl resorcinol n-hexyl resorcinol, n-heptylresorcinol, n-octyl resorcinol, n-nonyl resorcinol, phenyl resorcinolbenzyl resorcinol, phenylethyl resorcinol, phenylpropyl resorcinol,p-chlorobenzyl resorcinol, 5-chloro 2,4-dihydroxydiphenyl methane,4′-chloro 2,4-dihydroxydiphenyl methane, 5-bromo 2,4dihydroxydiphenylmethane, and 4′-bromo 2,4-dihydroxydiphenyl methane, bisphenoliccompounds like 2,2′-methylene bis(4-chlorophenol), 2,2′-methylenebis(3,4,6-trichlorophenol), 2,2′-methylene bis(4-chloro-6-bromophenol),bis(2-hydroxy-3,5-dichlorophenyl) sulphide, andbis(2-hydroxy-5-chlorobenzyl)sulphide, benzoic esters (parabens) likemethylparaben, propylparaben, butylparaben, ethylparaben,isopropylparaben, isobutylparaben, benzylparaben, sodium methylparaben,and sodium propylparaben, halogenated carbanilides (e.g.,3,4,4′-trichlorocarbanilides (Triclocarban® or TCC),3-trifluoromethyl-4,4′-dichlorocarbanilide, 3,3′,4-trichlorocarbanilide,etc.). The phenol based non-cationic antimicrobials are preferred. Thenon-cationic antimicrobial agent in the present invention is present inan amount from about 0.05 to about 15 wt %, preferably from about 0.1 toabout 5 wt %, and more preferably from about 0.5 to about 5 wt %.

Water soluble organic solvents include short chain (1 to 4 carbon atoms)alcohols, glycol ethers, and mixtures thereof. Such water solubleorganic solvents provide effective solubilization of many types ofgreases and fats which may be encountered in soils, as well as beinguseful in the solubilization of the pine oil in water, withoutsubstantially interfering with the blooming and scent characteristics ofthe compositions according to the present invention. Of course two ormore organic solvents may be used as the organic solvent constituentaccording to the invention. Examples of short chain alcohols includeethanol propanol, and isopropanol. Examples of such useful glycol ethersinclude propylene glycol methyl ether, dipropylene glycol methyl ether,tripropylene glycol methyl ether, propylene glycol n-propyl ether,diethylene glycol methyl ether, ethylene glycol butyl ether, diethyleneglycol methyl ether, and mixtures thereof. The short chain alcohols arepreferred. The water soluble organic solvent constituent may be presentin the concentrate compositions in amounts of from about 0.1 to about 20wt %, preferably in amounts of from about 0.5 to about 10 wt %.

Anionic soap surfactants represent the primary detergent component inthe present compositions of interest. This class of surfactants includesordinary alkali metal soaps such as the sodium, potassium, ammonium andalkanol-ammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms and preferably from about 10 to about 20 carbonatoms. Suitable fatty acids can be obtained from natural sources suchas, for instance, plant or animal esters (e.g., palm oil, coconut oil,babassu oil, soybean oil, castor oil, tallow, whale and fish oils,grease, lard, and mixtures thereof). The fatty acids also can besynthetically prepared (e.g., by the oxidation of petroleum, or by theFischer-Tropsch process). Resin acids are suitable such as rosin andthose resin acids in tall oil. Naphthenic acids are also suitable.Sodium and potassium soaps can be made by direct saponification of thefats and oils or by the neutralization of the free fatty acids which areprepared in a separate manufacturing process. Particularly useful is thesodium or potassium salt of the mixtures of fatty acids derived fromcastor oil, i.e., sodium or potassium castor oil soap.

The anionic soap surfactant can also comprise traditional anionicsurfactants such as alkali metal salts, ammonium salts, amine salts,aminoalcohol salts or the magnesium salts of one or more of thefollowing compounds: alkyl sulfates, alkyl ether sulfates,alkylamidoether sulfates, alkylaryl polyether sulfates, alkylarylsulfates, alkylaryl sulfonates, monoglyceride sulfates, alkylsulfonates,alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffinsulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates,alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates,alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acylisethionates, and N-acyl taurates. Generally, the alkyl or acyl radicalin these various compounds comprise a carbon chain containing 12 to 20carbon atoms. Of these anionic surfactants, the alkylaryl sulfonates arepreferred. From the anionic soap surfactants contemplated herein, thealkyl metal soaps, such as sodium or potassium castor oil soap, arepreferred.

The anionic soap surfactant in the present invention comprises an amountfrom about 0.1 to about 30 wt %, preferably from about 1 to about 20 wt%, and more preferably from about 2 to about 15 wt %.

Another component of the present invention is a hydrocarbon diluent,which is preferably an aromatic hydrocarbon diluent. For example, thehydrocarbon diluent may be Shellsolv AB, Aromatic 150, Chemical AbstractService (CAS) Registry No. 64742-94-5; Aromatic 200 (naphthalenedepleted), CAS Registry No. 64742-94-5; Aromatic 200, Aromatic 100, CASRegistry No. 64742-95-6; and HAN (heavy atmospheric naphtha) 857, CASRegistry No. 64742-06-9. Aromatic 200 is generally preferred. ShellsolvAB is commercially available from Shell Chemical Company. Aromatic 150,Aromatic 100, Aromatic 200 (naphthalene depleted), Aromatic 200, and HAN857 are commercially available from ExxonMobil. Other suitable aromaticsolvents are available from Koch Chemical, Ashland, Amoco, and Texaco aswell as the Isopar, Exxsol and Norpar aliphatic, isoparaffins andparaffins from ExxonMobil. The hydrocarbon diluent is preferably presentin the present composition in an amount of about 0.1 to about 15 wt %,preferably in an amount of from about 0.1 to about 10 wt % and morepreferably in an amount of from about 0.5 to about 5 wt %.

The compositions according to the present invention also comprise a pineoil constituent. Pine oil is an organic solvent, and is a complex blendof oils, alcohols, acids, esters, aldehydes and other organic compounds.These include terpenes which include a large number of related alcoholsor ketones. Some important constituents include terpineol, which is oneof three isomeric alcohols having the basic molecular formula C₁₀H₁₇OH.One type of pine oil, synthetic pine oil, will generally have a specificgravity, at 15.5° C. of about 0.9300, which is lower than the two othergrades of pine oil, namely steam distilled and sulfate pine oils, andwill generally contain a higher content of turpentine alcohols. Otherimportant compounds include alpha- and beta-pinene (turpentine), abieticacid (rosin), and other isoprene derivatives.

Particularly useful pine oils which are presently commercially availableinclude Unipine® 60 (from Union Camp, believed to contain approximately60% terpene alcohols), Unipine® S-70 and Unipine® S-70 (both arebelieved to contain approximately 70% terpene alcohols), Unipine® S andUnipine® 80 (both are believed to contain approximately 80% terpenealcohols), Unipine® 85 (which is believed to contain approximately 85%terpene alcohols), Unipine® 90 (which is believed to containapproximately 90% terpene alcohols), as well as Alpha Terpineol 90(which is believed to contain approximately 100% terpene alcohols).Further useful pine oils include Glidco®D Pine Oil™ 60 (available fromGlidco Organics Corp., Jacksonville, Fla., believed to containapproximately 60% terpene alcohols), Glidco® Pine Oil 140 (believed tocontain approximately 70% terpene alcohols), Glidco® Pine Oil 80(believed to contain approximately 80% terpene alcohols), Glidco® PineOil 150 (believed to contain approximately 85% terpene alcohols);Glidco® Terpene SW (believed to contain approximately 75% terpenealcohols); as well as Glidco® Terpineol 350 (believed to containapproximately 100% terpene alcohols). Other products which can containup to 100% pure alpha-terpineol, may also be used in the presentinvention.

Preferred as the pine oil constituent of the present invention are pineoil preparations which comprise at least about 60% terpene alcohols, andmore preferably those which comprise at least about 80% terpenealcohols.

The pine oil constituent may be present in the concentrate compositionsin amounts of from about 0.001 to about 20 wt %, preferably in amountsof from about 0.1 to about 15 wt % and more preferably from about 0.5 toabout 10 wt %.

As the concentrate compositions are aqueous, water forms a majorconstituent. Water is added in order to provide 100 wt % of theconcentrate composition. The water may be tap water, but is preferablydistilled and/or deionized water. If the water is tap water, it ispreferably appropriately filtered in order to remove any undesirableimpurities such as organics or inorganics, especially mineral saltswhich are present in hard water which may thus interfere with theoperation of the other constituents of the invention, as well as anyother optional components of the liquid concentrates according to theinvention.

Water is added in amounts which are sufficient to form the concentratedcompositions which amount is sufficient to ensure the retention of asubstantially clear characteristic when produced as a concentrate, butat the same time ensuring good blooming upon the addition of theconcentrated composition to a further amount of water, or upon theaddition of further water to the concentrate. This amount may be readilydetermined by first mixing measured amount of the non-water constituentsin a suitably sized vessel and then during stirring adding water.Generally, water is present in the concentrate compositions in amountsin excess of about 50 wt %, preferably in amounts of in excess of about70 wt %, but most preferably in amount of between 70-80 wt % based onthe total weight of the concentrate compositions according to theinvention.

As noted previously, the concentrate compositions according to theinvention may include further optional, but advantageously includedconstituents.

Useful optional constituents are one or more coloring agents which finduse in modifying the appearance of the concentrate compositions andenhance their appearance from the perspective of a consumer or other enduser. Known coloring agents, may be incorporated in the compositions ineffective amount to improve or impart to concentrate compositions anappearance characteristic of a pine oil type concentrate composition,such as a color ranging from colorless to yellow or yellow/brown colorwith or without fluorescent ingredients. Such a coloring agent orcoloring agents may be added in any useful amount in a conventionalfashion, i.e., admixing to a concentrate composition or blending withother constituents used to form a concentrate composition. However,other colors atypical of pine oil type and/or lemon oil type cleaningconcentrates may be used as well. Known art light stabilizerconstituents useful in pine oil type compositions may also be added,particularly wherein coloring agents are used in a composition. As isknown to the art, such light stabilizers act to retain the appearancecharacteristics of the concentrate compositions over longer intervals oftime.

Further useful optional constituents which may in some cases bedesirably included in the inventive compositions include rheologymodifying agents such as thickeners.

Other conventional additives known to the art but not expresslyenumerated here may also be included in the compositions according tothe invention. By way of non-limiting example these may includefragrance/fragrance adjusters (which do not interfere with the pine oilconstituent of the present invention (can generally be present in anamount of from about 0.000001 to about 1.5 wt % of the totalconcentrate, preferably non-pine oil based)), pH adjusters, pH bufferingagents, non-ionic surfactants and insect repellants. Such non-ionicsurfactants denoted here are conventionally known; examples aredescribed in McCutcheon's Detergents and Emulsifiers, North AmericanEdition, 2001; Kirk-Othmer, Encyclopedia of Chemical Technology, 4thEd., Vol. 23, pp. 478-541, the contents of which are herein incorporatedby reference. Such optional constituents should be selected so to havelittle or no detrimental effect upon the desirable characteristics ofthe present invention, namely the blooming behavior, cleaning efficacy,and disinfectant activity, low toxicity as provided by the inventivecompositions. Generally the total weight of such further conventionaladditives may comprise up to 10 wt % of a concentrated compositionformulation.

In certain preferred instances, one of the optional constituents, insectrepellants, may be a required component of an inventive composition.

Examples of insect repellants which can be used include those such asessential oils (such as, for example, oils of anise, citrus, aniseed,roses, mint, camphor, lemon, orange, rosemary, wintergreen, thyme,lavender, cloves, hops, tea tree, citronella, wheat, barley, lemongrass,cedar leaf, cedarwood, palmarosa, vetiver, sage, lime, juniper berry,cinnamon, fleagrass, geranium, sandalwood, violet, ginger, bergamot,marjoram, pepper, jasmine, chamomile, petitgrain, cranberry, eucalyptus,vervain, peppermint, gum benzoin, basil, fennel, fir, balsam, menthol,ocmea origanum, hydastis carradensis, berberidaceae daceae, ratanhiae,curcuma longa, Mentha arvensis (Cornmint), Mentha spicata (AmericanSpearmint), Mentha cardica (Scotch Spearmint), (−)-Limonene,(+)-Limonene, (−)-Carvone, Linalool, Alpha and Beta-Terpineol, Fencholicacid, Bomeol iso Bomeol, Bornyl acetate and iso Bomyl acetate. Alsoincluded in this class of natural essential oils are the key chemicalcomponents of the plant oils which have been found to provide theantimicrobial benefit. These chemicals include, but are not limited toanethol, catechole, camphene, pinocarvone, cedrol, thymol, eugenol,eucalyptol, ferulic acid, farnesol, hinokitiol, tropolone, limonene,menthol, methyl salicylate, carvacol, teipineol, verbenone, berberine,ratanhiae extract, caryophellene oxide, citronellic acid, curcumin,nerolidol and geraniol), N,N-diethyl-m-toluamide, diethyl phthalate,dimethyl phthalate, dibutyl phthalate, 2-Hydroxyethyl-n-octyl sulfide,N-Octyl bicycloheptene dicarboximide, Hexahydrodibenzofurancarboxaldehyde, Di-n-propyl isocinchomerate, 2-Ethyl-1,3-hexanediol,2-(n-butyl)-2-ethyl-1,3-propanediol, Dibutyl succinate, Piperonylbutoxide, Pyrethrum, certain fragrances, those agents listed in, forexample, U.S. Pat. No. 6,451,844, n-alkylneoalkanamides (such as thosedescribed in U.S. Pat. Nos. 5,006,562; 5,015,665; 5,143,900; 5,182,304;5,182,305; 5,258,408; 5,391,578; and 5,434,189; the disclosures of whichare incorporated herein by reference) where, for example,n-alkylneoalkanamide can have a formula of

-   -   wherein R₁, R₂, and R₃ are alkyl groups and the sum of the        carbon atoms therein is from 6 to 12, and wherein R₄ is either a        hydrogen atom or an alkyl group having one or two carbon atoms        and wherein R₅ is an alkyl group having one to three carbon        atoms.

When present, the insect repellant is present in the formulations of thepresent invention in an amount of from about 0.1 to about 5 wt %.

What is to be understood by the term “concentrate” and “concentratecomposition” in this specification and claims is the pre-consumerdilution and composition of the cleaning composition which is theessentially the form of the product prepared for sale to the consumer orother end user with required product shelf life. Such a consumer orother end user would then normally be expected to dilute the same withwater to form a cleaning composition. It is to be understood howeverthat nothing in this invention would bar its use as cleaning compositionwithout any further dilution and it may be used in the concentrations inwhich it was prepared for sale. Similarly, what is to be understood bythe term “cleaning compositions” are the water diluted compositionswhich are expected to be prepared by the consumer or other end user bymixing a measured amount of the “concentrate” with water in order toform an appropriately diluted cleaning composition which is suitable foruse in cleaning applications, especially in the cleaning of hardsurfaces.

It is also to be understood, that proportions of one or moreconstituents have been and generally are referred to as percent byweight or as parts by weight based on a measure of 100% by weight,unless otherwise indicated.

As generally denoted above, the formulations according to the inventioninclude both cleaning compositions and concentrates as outlined abovewhich differ only in the relative proportion of water to that of theother constituents forming such formulations. While the concentratedform of the cleaning compositions find use in their original form, theyare more frequently used in the formation of a cleaning compositiontherefrom. Such may be easily prepared by diluting measured amounts ofthe concentrate compositions in water by the consumer or other end userin certain weight ratios of concentrate:water, and optionally, agitatingthe same to ensure even distribution of the concentrate in the water. Asnoted, the concentrate may be used without dilution, i.e., inconcentrate:water concentrations of 1:0, to extremely dilute dilutionssuch as 1:2000. Desirably, the concentrate is diluted in the range of1:0.1-1:1000, preferably in the range of 1:10-1:500 but most preferablyin the range of 1:50-1:200. The actual dilution selected is in partdeterminable by the degree and amount of dirt and grime to be removedfrom a surface(s), the amount of mechanical force imparted to remove thesame, as well as the observed efficacy of a particular dilution.Generally better results and faster removal is to be expected at lowerrelative dilutions of the concentrate in water.

EXAMPLES

Preparation of Example Formulations:

Exemplary formulations illustrating certain preferred embodiments of theinventive compositions and described in more detail in Table I belowwere formulated generally in accordance with the following protocol.

Into a suitably sized vessel, a measured amount of the non-cationicantimicrobial agent (e.g., PCMX, DCMX was provided after which theremaining organic based components (e.g., hydrocarbon diluent, pine oil,water soluble organic solvent, dye (if any). These components werestirred until the non-cationic antimicrobial agent was fully dissolved.The anionic soap surfactant is then added to the organic solution andthe components are stirred until the mixture is homogeneous. Theremaining amount of water is then added to the organic/anionic soapsurfactant mixture and the components are then mixed until the solutionis clear and homogeneous. Mixing of the various components at thevarious times can range from 5 minutes to 120 minutes, depending on thevolume of the mixture; the amount of time can vary so long as particularsolutions appeared to be homogeneous. The exemplary compositions werereadily pourable, and retained well mixed characteristics (i.e., stablemixtures) upon standing for extended periods, even in excess of 90 days.The exemplary compositions are also stable at elevated temperatures upto 120° F. for several weeks.

Examples of inventive formulations are shown in Table 1 below. TABLE 1Components Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Aromatic 200 4.001.50 1.50 0.00 1.50 1.00 0.30 Pine Oil 80 1.00 1.00 2.00 1.00 2.00 3.50PCMX¹ 10.00 1.50 1.50 1.50 0.00 1.40 DCMX² 1.50 OBPCP 1.50 IPA³ 4.002.00 2.00 3.00 2.00 3.00 Na COS⁴ 12.93 20.00 20.00 35.00 20.00 35.0020.00 SDS⁵ 0.80 SLS⁶ 3.00 NP-9 0.60 Insect repellant⁷ 0.40 4.00 0.405.00 Dye (1%) 0.25 Water, DI 68.27 73.75 73.60 54.50 73.60 52.00 71.70Total 100.01 100.00 100.00 100.00 100.00 100.00 100.00 Components Ex. 8Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Aromatic 200 1.50 0.30 0.50 1.50 1.500.00 Aromatic 200 (naphthalene 0.40 depleted) Pine Oil 80 or 85 1.003.00 2.00 0.80 1.60 2.00 PCMX 1.40 0.00 0.00 1.50 1.50 1.50 OBPCP⁸ 1.501.50 IPA 2.00 3.00 3.00 2.00 2.00 3.00 Na COS 18.00 18.00 20.00 20.0020.00 35.00 NP-9⁹ 1.00 Insect repellant 0.40 0.40 0.40 Fragrance Oils¹⁰0.25 0.20 0.40 Water, DI 76.10 74.20 72.00 73.60 72.60 54.10 Total100.00 100.00 100.00 100.00 100.00 100.00¹p-chloro-m-xylene²dichloro meta xylenol³isopropanol⁴sodium castor oil soap (40%)⁵sodium dodecyl benzene sulfonate (40%)⁶sodium lauryl suflate (30%)⁷dimethyl phthalate⁸ortho-benzyl-para-chlorophenol⁹nonylphenol ethoxylates (9 moles EO)¹⁰lemongrass oil or eucalyptus oil

The compositions of the present invention were evaluated for bloom,cleaning and disinfecting properties.

The formulations according to Ex. 1 through Ex. 13 are clear (althoughsome examples contain dye but these dyes do not affect the clarity ofthe compositions), but when diluted at ratios of 1 part to 100 parts or200 parts of water at both 20° C. and 35° C., in the as mixed aqueousdilutions are expected to achieve the targeted loss of lighttransmittance of about 40% and more. Ex. 2, with and without insectrepellant, was tested for bloom. In certain regions of the world wherecold water is used for cleaning purposes, formulations of the presentinvention can achieve a loss of light transmission greater than 90%.

Light transmittance values closer to zero indicate improved bloomingbehavior. The protocol for evaluating light transmittance is describedas follows: The results of the light transmittance evaluation wasdetermined as a percentage of light transmitted through a sample of aparticular aqueous dilution wherein the transmission of a like sample ofwater is assigned a percentage of 100%. Testing was performed bypreparing a 1:100 or 1:200 dilution of the example formulation:water,(tap water) after which the sample was mixed for 30 seconds and atransmittance reading was taken using a Brinkman model PC801 dippingprobe colorimeter, which was set at 620 nm to determine the lighttransmission of each of the samples. Readings were taken at watertemperatures of 20° C. and at 35° C. were evaluated, as well as thereference (pure tap water) sample used to calibrate the calorimeter tothe reference 100% light transmission sample outlined above. The resultsare shown in Table 2 below. TABLE 2 Composition 1:100 1:200 In water at20° C. Ex. 2 w/IR¹ 0.5 1.3 Ex. 2 w/o IR 0.4 1.1 In water at 35° C. Ex. 2w/IR 34.6 50.6 Ex. 2 w/o IR 31.3 61.7¹IR is an insect repellant

These results provide an empirical evaluation of the degree oftransparency of a diluted example formulation wherein 0% indicatescomplete opacity and 100% the transparency of the sample. Accordingly, alower reported light transmittance value of a particular aqueousdilution provided a more desirable indication of the bloomingcharacteristic of the particular aqueous dilution. It can be noted thatin some instances, warm water will be “soft” and cold water will be“hard.” In the above table, the warm (35° C.) water was treated (or“soft”) and thus the blooming characteristics are somewhat reduced.However, if non-softened warm water were used, similar bloomingcharacteristics to those seen in cold water would be achieved.

Cleaning Evaluations

Cleaning evaluations were performed in accordance with the testingprotocol outlined according to ASTM D4488 AZ Test Method, whichevaluated the efficacy of the cleaning compositions on masonitewallboard samples painted with wall paint. The soil applied was a greasysoil sample containing vegetable oil, food shortening and animal fat.The sponge (water dampened) of a Gardner Abrasion Tester apparatus wassquirted with a 15 gram sample of a tested cleaning composition, and theapparatus was cycled 10 times. The evaluation of cleaning compositionswas “paired” with one side of each of the test samples treated with acomposition according to the invention, and the other side of the samesample treated with a comparative example's composition, thus allowing a“side-by-side” comparison to be made. Each of these tests wereduplicated on 5 wallboard tiles and the results statistically analyzedand the averaged results reported on Table 3, below. The cleaningefficacy of the tested compositions was evaluated utilizing a MinoltaChroma Meter CF-110, with Data Processor DP-100, which evaluatedspectrophotomic characteristics of the sample. The results are reportedon Table 3, following. TABLE 3 Composition Average % Soil Removal Ex. 290.05 Dettol Multi-Purpose Disinfectant 91.45 from Reckitt BenckiserDomex Disinfectant Cleaner from 57.64 Lever Johnson Domex 2-in-1Phenolic Cleaner 69.55 from Lever Johnson Lizol Pineol ShaktiDisinfectant 87.25 Cleaner from Reckitt Benckiser

With respect to the results reported on Table 3 a value of “100” isindicative of total soil removal and a “0” value is indicative no soilremoval. As can be seen from the results of Table 3, the cleaningefficacy of the composition according to the invention generallyprovided superior results or were on parity with those of known artcleaning products.

Evaluation of Antimicrobial Efficacy

Representative compositions of the present invention were evaluated inorder to evaluate their antimicrobial efficacy against Staphylococcusaureus (gram positive type pathogenic bacteria) (ATCC 6538), andSalmonella choleraesuis (gram negative type pathogenic bacteria) (ATCC10708). The testing was performed generally in accordance with theprotocols outlined in “Use-Dilution Method” as promulgated by theAssociation of Official Analytical Chemists (AOAC).

The results of the AOAC Use-Dilution Test Method indicates the number oftest substrates wherein the tested organism remains viable after contactfor 10 minutes with a test disinfecting composition/total number oftested substrates (plates) evaluated in accordance with the AOACUse-Dilution Test. Thus, a result of “0/10” indicates that of 10 testsubstrates bearing the test organism and contacted for 10 minutes in atest disinfecting composition, 0 test substrates had viable (live) testorganisms at the conclusion of the test. Such a result is excellent,illustrating the excellent disinfecting efficacy of the testedcomposition.

Results of the antimicrobial testing are indicated on Table 4, below.The reported results indicate the number of test plates with live testorganisms/number of test plates tested for each example formulation andorganism tested. TABLE 4 Composition (dilution) S. aureus S.choleraesuis Ex. 3 (1:50) 0/10 Not tested Ex. 7 (1:20) 0/10 0/10

Composition Ex. 3 with added dye was evaluated at three dilutions (1:60;1:90; and 1:100 compositions:water) using the Biomek® 2000 LaboratoryAutomation Workstation together with the BioWorks Operating System(available from Beckman Coulter Inc., Fullerton, Calif.) with the aboveorganisms at a concentration of 9 logs. The Biomek simulates a microbialreduction suspension test. One part of organism suspension(Staphylococcus aureus or Salmonella choleraesuis) is added to certaindilutions of Ex. 3 in an appropriate container. Deionized water (DI H₂O)was used a control. The organism and sample are then mixed thoroughlyfor 15 seconds. Serial tenfold dilutions are carried out in aneutralizing broth. The diluted samples are then incubated for 2448hours at 35-37° C. Thereafter, surviving organisms are quantified andLog10 reduction, as a measurement of organism survivors are calculatedas follows:Log10 Reduction=(Log10 Survivors/DI H₂O Control)−(Log10Survivors/Sample)

For this test with a contact time of 15 second, a Log10 reduction valueof 3 or greater against both organisms is a good indication ofacceptable performance (i.e., broad spectrum antimicrobial activity).The results of this evaluation are summarized in Table 5 below. TABLE 5Organism/dilution 1:60 1:90 1:100 S. aureus >6 log 6.7 3.99 S.choleraesuis >6 log 4.03 2.7

Various compositions were tested for insect repellency (against Americancockroach (Periplaneta americana) on either vinyl flooring or mosaicflooring. In either using vinyl flooring or mosaic flooring, a 100cm×100 cm square was treated with the compositions at twoconcentrations: neat and at 5 ml composition/1000 ml water. Thecompositions were applied to the surface and allowed to dry for 30minutes.

The treated surface (either vinyl or mosaic) was placed in one half of asuitably sized tray with a similar sized untreated surface placed in theother half of the tray. At the center of each surface (treated anduntreated) were placed two 30 cm×30 cm sheets of Formica® to act as acockroach harborage. The Formica® sheet in the treated section wastreated at the same rate as the treated surface.

Fifty cockroaches (15 adults, 35 nymphs) were placed in the middle ofthe tray. No food or water was supplied to the cockroaches.

At the end of thirty minutes, 3 hours, 6 hours, and 12 hours, the numberof cockroaches under each Formica® harborage was counted.

Each assay was repeated three times with three replicates each time. Thedata are shown below in Tables 6, 6A, 7, and 7A. TABLE 6 Formulationstested Neat on Vinyl Flooring The number of cockroaches present in eachharborage of treated and untreated vinyl flooring surfaces in differenttime intervals (each value is the mean of three individual observations)Time in hours Trial 30 minutes 3 hours 6 hours 12 hours Ex. No. T Un. TT Un. T T Un. T T. Un. T Ex. 5 I 4 14 8 20 14 20 26 24 II 6 16 15 22 1625 16 32 III 3 20 12 23 16 24 18 29 Ex. 4 I 3 19 7 23 15 26 26 24 II 116 10 24 18 22 24 26 III 1 18 13 21 19 24 20 29 Ex. 3 I 8 19 12 22 18 2327 18 II 4 17 17 21 16 27 20 26 III 6 16 14 22 17 21 22 24

TABLE 6A Formulations tested 5 ml Ex./1000 ml water on Vinyl FlooringThe number of cockroaches present in each harborage of treated anduntreated vinyl flooring surfaces in different time intervals (eachvalue is the mean of three individual observations) Time in hours Trial30 minutes 3 hours 6 hours 12 hours Ex. No. T Un. T T Un. T T Un. T TUn. T Ex. 5 I 8 12 22 15 25 22 31 18 II 10 15 22 18 22 24 23 24 III 9 1618 21 25 23 20 26 Ex. 4 I 11 15 17 22 23 20 31 19 II 10 13 19 26 20 2820 28 III 10 20 12 26 18 26 20 28 Ex. 3 I 13 15 19 22 20 22 24 24 II 1516 26 22 25 23 20 27 III 12 18 23 18 27 19 20 20

TABLE 7 Formulations tested Neat on Mosaic Flooring The number ofcockroaches present in each harborage of treated and untreated mosaicflooring surfaces in different time intervals (each value is the mean ofthree individual observations) Time in hours Trial 30 minutes 3 hours 6hours 12 hours Ex. No. T Un. T T Un. T T Un. T T Un. T Ex. 5 I 2 18 8 2414 26 23 27 II 1 14 9 26 17 28 24 26 III 0 16 11 28 20 24 21 29 Ex. 4 I6 12 10 19 15 21 25 25 II 5 18 16 23 18 24 22 28 III 2 21 11 24 17 23 2425 Ex. 3 I 7 18 14 23 16 23 21 29 II 6 14 17 27 17 27 19 26 III 4 16 1321 18 21 24 23

TABLE 7A Formulations tested 5 ml Ex./1000 ml water on Mosaic FlooringThe number of cockroaches present in each harborage of treated anduntreated mosaic flooring surfaces in different time intervals (eachvalue is the mean of three individual observations) Time in hours Trial30 minutes 3 hours 6 hours 12 hours Ex. No. T Un. T T Un. T T Un. T TUn. T Ex. 5 I 12 15 18 22 19 22 22 24 II 10 16 19 26 22 26 24 26 III 921 21 26 23 26 20 26 Ex. 4 I 9 14 20 19 20 22 20 24 II 10 19 22 24 25 2425 24 III 12 21 21 21 21 25 22 25 Ex. 3 I 11 18 24 19 24 21 24 23 II 1616 27 22 25 23 22 24 III 14 20 23 22 23 22 20 23

1. A hard surface cleaning concentrate composition comprising: a) fromabout 0.05 to about 10 wt % of a non-cationic antimicrobial agent; b)from about 1 to about 20 wt % of a water soluble organic solvent; c)from about 1 to about 20 wt % of an anionic soap surfactant; d) fromabout 1 to about 15 wt % of an hydrocarbon diluent; e) from about 0.001to about 20 wt % of pine oil which is at least 60% terpene alcohols; f)optionally, from about 0 to about 10 wt % of optional materials selectedfrom dyes, colorants, pH stabilizers and buffers, non-ionic surfactants,fragrance/fragrance enhancers, viscosity modifiers, insect repellants,and light stabilizers; and g) the balance being water.
 2. The cleaningconcentrate of claim 1 wherein the non-cationic antimicrobial agent isselected from pyrithiones, dimethyldimethylol hydantoin,methylchloroisothiazolinone/methylisothiazolinone sodium sulfite, sodiumbisulfite, imidazolidinyl urea, diazolidinyl urea, benzyl alcohol,2-bromo-2-nitropropane-1,3-diol, formal in (formaldehyde), iodopropenylbutylcarbamate, chloroacetamide, methanamine, methyldibromonitrileglutaronitrile, glutaraldehyde, 5-bromo-5-nitro-1,3-dioxane, phenethylalcohol, o-phenylphenol/sodium o-phenylphenol, sodiumhydroxymethylglycinate, polymethoxy bicyclic oxazolidine, dimethoxane,thimersal dichlorobenzyl alcohol, captan, chlorphenenesin,dichlorophene, chlorbutanol, glyceryl laurate, halogenated diphenylethers, phenolic compounds, mono- and poly-alkyl and aromatichalophenols, resorcinol and its derivatives, bisphenolic compounds,benzoic esters (parabens), halogenated carbanilides,3-trifluoromethyl-4,4′-dichlorocarbanilide, and3,3′,4-trichlorocarbanilide.
 3. The cleaning concentrate of claim 2wherein the non-cationic antimicrobial agent is a mono- and poly-alkyland aromatic halophenol selected from the group p-chlorophenol, methylp-chlorophenol, ethyl p-chlorophenol, n-propyl p-chlorophenol, n-butylp-chlorophenol, n-amyl p-chlorophenol, sec-amyl p-chlorophenol, n-hexylp-chlorophenol, cyclohexyl p-chlorophenol, n-heptyl p-chlorophenol,n-octyl p-chlorophenol, o-chlorophenol, methyl o-chlorophenol, ethylo-chlorophenol, n-propyl o-chlorophenol, n-butyl o-chlorophenol, n-amylo-chlorophenol, tert-amyl o-chlorophenol, n-hexyl o-chlorophenol,n-heptyl o-chlorophenol, o-benzyl p-chlorophenol, o-benzyl-m-methylp-chlorophenol, o-benzyl-m, m-dimethyl p-chlorophenol, o-phenylethylp-chlorophenol, o-phenylethyl-m-methyl p-chlorophenol, 3-methylp-chlorophenol, 3,5-dimethyl p-chlorophenol, 6-ethyl-3-methylp-chlorophenol, 6-n-propyl-3-methyl p-chlorophenol,6-iso-propyl-3-methyl p-chlorophenol, 2-ethyl-3,5-dimethylp-chlorophenol, 6-sec-butyl-3-methyl p-chlorophenol,2-iso-propyl-3,5-dimethyl p-chlorophenol, 6-diethylmethyl-3-methylp-chlorophenol, 6-iso-propyl-2-ethyl-3-methyl p-chlorophenol,2-sec-amyl-3,5-dimethyl p-chlorophenol 2-diethylmethyl-3,5-dimethylp-chlorophenol, 6-sec-octyl-3-methyl p-chlorophenol, p-chloro-m-cresol,p-bromophenol, methyl p-bromophenol, ethyl p-bromophenol, n-propylp-bromophenol, n-butyl p-bromophenol, n-amyl p-bromophenol, sec-amylp-bromophenol, n-hexyl p-bromophenol, cyclohexyl p-bromophenol,o-bromophenol, tert-amyl o-bromophenol, n-hexyl o-bromophenol,n-propyl-m,m-dimethyl o-bromophenol, 2-phenyl phenol, 4-chloro-2-methylphenol, 4-chloro-3-methyl phenol, 4-chloro-3,5-dimethyl phenol,2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-terabromo-2-methylphenol,5-methyl-2-pentylphenol, 4-isopropyl-3-methylphenol,para-chloro-meta-xylenol, dichloro meta xylenol, chlorothymol, and5-chloro-2-hydroxydiphenylmethane,
 4. The composition of claim 1 whereinthe water soluble organic solvent is selected from C1-4 alcohols, glycolethers, and mixtures thereof.
 5. The composition of claim 1 wherein theanionic soap surfactant is selected from alkali metal soap fatty acidscontaining from about 8 to about 24 carbon atoms, alkali metal salts,ammonium salts, amine salts, aminoalcohol salts or the magnesium saltsof one or more of the following compounds: alkyl sulfates, alkyl ethersulfates, alkylamidoether sulfates, alkylaryl polyether sulfates,alkylaryl sulfates, alkylaryl sulfonates, monoglyceride sulfates,alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates,olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkylether sulfosuccinates, alkylamide sulfosuccinates, alkylsulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl etherphosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates.6. The composition of claim 5 wherein the anionic soap surfactant isselected from alkali metal soap fatty acids.
 7. The composition of claim1 wherein the hydrocarbon diluent is an aromatic hydrocarbon diluentselected from Shellsolv AB, Aromatic 150, Aromatic 200 (naphthalenedepleted), Aromatic 200, Aromatic 100, and HAN
 857. 8. The compositionof claim 1 wherein the non-cationic antimicrobial agent is present in anamount of from about 0.1 to about 5 wt %.
 9. The composition of claim 1wherein the water soluble organic solvent is present in an amount offrom about 0.5 to about 10 wt %.
 10. The composition of claim 1 whereinthe anionic soap surfactant is present in an amount of from about 1 toabout 20 wt %.
 11. The composition of claim 1 wherein the hydrocarbondiluent is present in an amount of from about 0.1 to about 10 wt %. 12.The composition of claim 1 wherein the pine oil is present in an amountof from about 0.1 to about 15 wt %.
 13. (canceled)
 14. (canceled) 15.The cleaning concentrate according to claim 1 which contain one or moreinsect repellants.
 16. The cleaning concentrate of claim 15 wherein theamount of one or more insect repellant ranges from about 0.1 to about 5wt %.
 17. (canceled)
 18. (canceled)
 19. (canceled)
 20. (canceled) 21.(canceled)
 22. (canceled)
 23. (canceled)
 24. (canceled)
 25. (canceled)26. (canceled)
 27. (canceled)
 28. (canceled)
 29. A hard surface cleaningconcentrate composition according to claim 1 comprising: a) from about0.1 to about 5 wt % of a non-cationic antimicrobial agent; b) from about0.5 to about 10 wt % of a water soluble organic solvent; c) from about 1to about 20 wt % of an anionic soap surfactant; d) from about 0.1 toabout 10 wt % of an hydrocarbon diluent; e) from about 0.1 to about 15wt % of pine oil which is at least 60% terpene alcohols; f) from about0.1 to about 5 wt % of one or more insect repellants; and g) the balancebeing water.
 30. (canceled)
 31. The cleaning concentrate according toclaim 15 one or more insect repellents is selected from essential oilsselected from oils of anise, citrus, aniseed, roses, mint, camphor,lemon, orange, rosemary, wintergreen, thyme, lavender, cloves, hops, teatree, citronella, wheat, barley, lemongrass, cedar leaf, cedarwood,cinnamon, fleagrass, geranium, sandalwood, violet, cranberry,eucalyptus, vervain, peppermint, gum benzoin, basil, fennel, fir,balsam, menthol, ocmea origanum, hydastis carradensis, berberidaceaedaceae, ratanhiae, curcuma longa, Mentha arvensis (Cornmint), Menthaspicata (American Spearmint), Mentha cardica (Scotch Spearmint),(−)-Limonene, (+)-Limonene, (−)-Carvone, Linalool, Alpha andBeta-Terpineol, Fencholic acid, Bomeol iso Borneol, Bornyl acetate andiso Bornyl acetate and related chemical components of the plant oilsselected from anethol, catechole, camphene, pinocarvone, cedrol, thymol,eugenol, eucalyptol, ferulic acid, farnesol, hinokitiol, tropolone,limonene, menthol, methyl salicylate, carvacol, terpineol, verbenone,berberine, ratanhiae extract, caryophellene oxide, citronellic acid,curcumin, nerolidol and geraniol; N,N-diethyl-m-toluamide, diethylphthalate, dimethyl phthalate, dibutyl phthalate, 2-Hydroxyethyl-n-octylsulfide, N-Octyl bicycloheptene dicarboximide, Hexahydrodibenzofurancarboxaldehyde, Di-n-propyl isocinchomerate, 2-Ethyl-1,3-hexanediol,2-(n-butyl)-2-ethyl-1,3-propanediol, Dibutyl succinate, Piperonylbutoxide, Pyrethrum, fragrances, n-alkylneoalkanamides having a formulaof

wherein R₁, R₂, and R₃ are alkyl groups and the sum of the carbon atomstherein is from 6 to 12, and wherein R₄ is either a hydrogen atom or analkyl group having one or two carbon atoms and wherein R₅ is an alkylgroup having one to three carbon atoms.